Quaternized reactive phthalocyanine dyestuffs containing triazine and nicotinic acid groups

ABSTRACT

REACTIVE TRIAZINE DYESTUFFS HAVING THE FORMULA:   2-((3-((NA-O3S-)N-CHROMOGEN-SO2-NH-),6-(NA-O3S-)PHENYL)   -NH-),4-((NA-OOC-)M-PYRIDINIUM,6-((X-PHENYL)-N(-CH2-   SO3-NA)-)-S-TRIAZINE CL(-)   WHEREIN CHROMOGEN IS A PHTHALOCYANINE DYESTUFFS RESIDUE, X IS SELECTED FROM THE GROUP CONSISTING OF H, CH3, OCH3 AND OC2H5, N IS AN INTEGER FROM 1 TO 4, AND M IS 1 OR 2, ARE EFFECTIVE FOR DYEING CELLULOSE FIBERS. THE DYESTUFFS MAY BE ABSORBED AND FIXED ONTO THE CELLULOSE FIBERS BY KNOWN HOT OR COLD DYEING TECHNIQUES. INTENSE DYEINGS HAVING VERY GOOD FASTNESS TO WASHING ARE OBTAINED.

United States Patent 3,642,787 QUATERNIZED REACTIVE PHTHALOCYANINEDYESTUFFS CONTAINING TRIAZINE AND NICOTINIC ACID GROUPS Sandro Ponzini,Saronno, Paolo Castelli, Monza, and Jean Stanislao Lawendel, Milan,Italy, assignors to iaziende Colori Nazionali Aflini ACNA S.p.A., Milan,

ta y No Drawing. Original application June 5, 1968, Ser. No. 749,899.Divided and this application Mar. 19, 1970, Ser. No. 21,221

Int. Cl. C07d 55/22 US. Cl. 260-242 Claims ABSTRACT OF THE DISCLOSUREReactive triazine dyestuffs having the formula:

(COONzUm wherein chromogen is a phthalocyanine dyestuif residue, X isselected ifrorn the group consisting of H, CH OCH and OC H n is aninteger from 1 to 4, and m is 1 or 2, are eifective for dyeing cellulosefibers. The dyestulfs may be absorbed and fixed onto the cellulosefibers by known hot or cold dyeing techniques. Intense dyeings havingvery good fastness to washing are obtained.

CROSS REFERENCE TO RELATED APPLICATIONS This application is a divisionof copending application Ser. No. 749,899, filed June 5, 1968, now USPat. 3,522,232, which application is a division of application Ser. No.472,668, filed July 16, 1965, now US. Pat. 3,416,875.

BACKGROUND OF THE INVENTION (1) Field of the invention This inventionrelates to a series of reactive triazine dyestuffs capable of beingabsorbed and chemically fixed on cellulose fibers by either a cold orwarm dyeing process.

(2) Description of the prior art Various classes of dyestuifs havingreactive groups capable of forming such bonds are already known. Theseinclude dyestuffs containing at least one of the following reactivegroups: monochlorotriazinyl, dichlorotri'azinyl, trichloropyrimidyl,vinylsulfonic, and dichloroquinoxalyl. The dyeing conditions forapplying these dyestuffs varies according to the nature of the groupspresent.

SUMMARY OF THE INVENTION The dyestuffs of the present invention areprepared by 3,642,787 Patented Feb. 15, 1972 quaternizing a reactivetriazine dyestutf having the general formula:

(S 013N231) I w es ! N on, X some wherein X is selected from the groupconsisting of H, CH OCH and OC H n is an integer from 1 to 4, and thechromogen is the colored residue of a phthalocyanine dyestuif.

The reactive quaternized dyestuffs of the present invention have thegeneral formula:

( sNa) n I (COONa)m wherein chromogen, m, X and n are as defined above.The reactive quaternized dyestufis of the present invention may beprepared by reacting a metal salt of a nicotinic acid with the reactivedyestuif of the general Formula I.

DESCRIPTION OF THE PREFERRED EMBODIMENT More particularly, the dyestuffsof the present invention have the formula:

wherein Fe is copper phthalocyanine, Y is SO NH p is 0 or 0.5, and n isan integer from 1 to 4.

The reactive dyestuffs of the present invention have improvedcharacteristics for applications in dyeing with remarkably increaseddyeing yields and possess the further advantage that they may be used byboth cold and warm dyeing applications. It is quite unexpected that byquaternizing the dyestuifs of the general Formula I with a metal salt ofisonicotinic acid, dyeing yields higher than those obtained by the useof a dyeing catalyst based on other organic tertiary amines can beobtained using the cold application method. This is particularlysurprising with respect to the aliphatic tertiary amines, such asasymmetric dimethylhydrazine, since it is known that thehydrosolubilizing substituents (SO H, COOH) diminish the affinity ofdyestufis for cellulose fibers.

Also, using the dyestuffs of therpresent invention in a warm dyeingapplication, i.e., -60-90 C., the dyeing yields on cellulose aresubstantialy improved over those obtained with the prior art dyestuffs.

The use of isonicotinic acid as the quaternizing agent of the abovementioned chlorotriazine dyestuffs generally produces the followingadvantages with respect to the use of other quaternizable tertiaryamines, namely:

(1) Dyeing of cellulose fibers by the cold process without adding dyeingcatalysts.

(2) Increasing remarkably, in most cases, the dyeing yields,particularly in the cold dyeing process, even when compared to the useof known dyeing catalysts based on aliphatic tertiary amines.

(3) In contrast to the other tertiary amines, isonicotinic acid isodorless, and therefore the dye baths, both cold and warm, arecompletely free of disagreeable or irritating odors.

(4) Increasing of the dye solubility in the cases where it isparticularly poor.

(5) Possibility of dyeing cellulose materials in a Warm dye bath bygenerally used processes, using the same quaternized dyes in thoseparticular cases where practical considerations might suggest thismethod as the preferable one.

The use of isonicotinic acid, also from the point of view of costs, isadvantageous because the excess isonicotinic acid used in thequaternization reaction may be easily recovered from the mother liquorsby filtration, after acidification of these mother liquors, and then itmay be reused.

The quaternization reaction is generally carried out by dissolving thereactive phthalocyanine dyestutf in a 2% solution of a metal salt of theisonicotinic acid.

The reaction temperature may be varied within wide limits but it ispreferably kept between 60 and 80 C. The reaction rate is obviouslyinfluenced by the selected temperature and may be monitored bychromatographic analysis.

The following examples serve to further illustrate the present inventionwithout in any way limiting the scope thereof:

EXAMPLE 1 2 parts of isonicotinic acid and 0.64 part of 100% NaOH aredissolved in 100 parts of water at 80 C. 4 parts of the dyestutf:

(I) SO Na wherein Pc means copper phthalocyanine, are added to thesolution.

The solution is maintained at this temperature for one night (abouthours), and then the dyestuff is separated by direct drying at about 60C.

A dyestutf having the following formula is obtained:

wherein Pc means copper phthalocyanine.

The obtained dyestutf dyes cotton at a temperature of 60 C., with goodtinctorial yields, in a turquoise shade having good fastness to Washing.The dyestuff to be quaternized used in this process can be obtained asfollows:

0.1 mol of the intermediate having the following structure:

wherein Pc means copper phthalicyanine, are added under agitation, inthe form of a paste, in 2000 parts of water and the pH is adjusted to avalue of 8 by adding small amounts of NaOH.

The solution thus obtained is slowly added at 05 C. to a solution (whichis also kept at 0-5 C.) of the condensation product of 0.1 mol ofcyanuric chloride and 0.1 mol of the sodium salt of the anilinomethanesulfonic acid added with 10 parts of sodium bicarbonate.

(The condensation product of cyanuric chloride and the sodium salt ofthe anilino methanesulfonic acid can be prepared, for instance, bydissolving, in 500 parts of water, 0.1 mol of the sodium salt of theanilino methanesulfonic acid and adding 17 parts of sodium bicarbonateand successively, at a temperature of 0-5 C., a suspension (kept at 05C.) of 0.1 mol of cyanuric chloride in 1500 parts of water).

The whole is agitated for some hours at increasing temperature up to2025 C., until a sample shows that the reaction is complete.

The reaction product is separated by salting.

EXAMPLE 2 By working as described in the preceding example, but usingthe dyestuff having the structure:

( 2 H2)o.s

(I) SO Ha wherein Pc means copper phthalocyanine, a quaternized dyestuffis obtained having characteristics similar to those of the dyestutf ofExample 1. The dyestutf has the following formula:

C SO NZI wherein Pc means copper phthalocyanine.

EXAMPLE 3 A dye bath is prepared by dissolving 2 parts by weight of thedyestulf prepared according to the Example 2, in 2000 parts by volume ofwater at the temperature of 60 C.

parts of the cellulose material are introduced in the dye bath; after 15minutes, 60 parts of anhydrous Na SO are added; after 45 minutes, 15parts of Na CO are added; after 60 minutes, 15 parts of Na CO are added.

The bath is maintained at 60 C. for one further hour, in order tocomplete the fixing of the dyestulf and then the material is soaped for30 minutes at the boiling point with a 3% soap solution.

A cellulose material dyed in a turquoise shade having very good fastnessto Wet treatment is obtained with very good tinctorial yields.

Variations and modifications can, of course, be made without departingfrom the spirit and scope of the invention.

Having thus described the invention, what is desired to be secured byLetters Patent and is hereby claimed is:

1. A reactive dyestuff having the formula:

wherein Pc is a phthalocyanine residue, Y is SO NH p is or 0.5, n is aninteger from 1 to 4 and m is 1 or 2.

2. The reactive dyestufi as claimed in claim 1 and having th estructure:

N CH2 3. The reactive dyestulf as claimed in claim 1, and having thestructure:

4. The reactive dyestuff as claimed in claim 2 wherein Fe is copperphthalocyanine.

5. The reactive dyestufi? as claimed in claim 3 wherein Pc is copperphthalocyanine.

References Cited UNITED STATES PATENTS 3/ 1964 Tartter et a1, 2602429/1965 Benz et -al 260-153 UNITED STATES PATENT OFFICE CERTIFICATE OFCORRECTION Patent No. 3,642,787 Dated February 15, 1972.

Inventor-(s) Sandro Ponzini, Paolo Castelli &.Jean Stanislao Lawendel Itis certified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

I' I Column 1, line 32: "chromogen" should read Chromogen Column 2, line15: "chromogen" should read Chromogen Column 2, line 31: "chromogen"should read Chromogen Column 2, third structural formula, line 46, thatportion of the formula reading CH should read iH ll SO NS. SO Na Column3, line 3: "substantialy" should read substantially Column 3, line 27:"of costs," should read of cost,

Column 3, second structural formula, line. 63, that portion of theformula reading should read.

III

' Column 4, line 11: "phthalicyanine" should read phthalocyanine Column4, second structural formula, line 43, that portion of the formulareading CH2 should read 21-1 L O Ha" I SO Na J *zg gg g V SiXI lilflTENT kfi CERTIFICATE OF CORRECTION Patent No. 3, 642, 787 DatedFebruary 15, 1972 Inventor(s) Sandro Ponzini, Paolo Castelli 8: JeanStanislao Lawendel It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

[ PAGE 2 I Column 4, line 70: After "are added;" (first occurrence),insert after 30 minutes, 60 parts of anhydrous Na SO are added; Column5, the structural formula in Claim 1, line 15, that portion of theformula reading H should read Column 5, Claim 2, line 243 "th e" shouldread the.

Signed and sealed this 27th day of June 1972.

(SEAL) Atteet:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents

